2-carbamyl-2-imidazolines and method for their production

ABSTRACT

Production of 2-carbamyl-2-imidazolines by reacting haloacetamides with 1,2-alkylene diamines and elementary sulfur, and the 2-carbamyl-2-imidazolines. The new compounds are auxiliaries for the textile and leather industries, plant protection agents and valuable starting material for the manufacture of textile and leather auxiliaries and plant protection agents.

United States Patent Hagen et al.

[451 Aug. 1,1972

[ Z-CARBAMYL-Z-IMIDAZOLINESAND METHOD FOR THEIR PRODUCTION [72]Inventors: Helmut Hagen, Frankenthal; Friedrich Becke, Heidelberg, bothof Germany [73] Assignee: Badische Anilin- & Soda-FahrikAktiengesellschaft, Ludwigshafen,

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[22] Filed: April 22,1970 21 Appl.No.: 30,935

[30] Foreign Application Priority Data April 26, 1969 Germany ..P 19 21341.3

[52] U.S.Cl ..260/247.5 R,1l7/138.8 R,

269 292 51 Int. Cl. ..C07d 49/34 [58] Field of Search ..260/309.6, 247.5R, 268 c,

[56] References Cited UNITED STATES PATENTS 3,147,275 9/1964Fruhstorferetal. ..260/309.6 3,365,462 1/1968 Holanetal. ..260/309.6

FOREIGN PATENTS OR APPLICATIONS 229,606 2/ I 944 Switzerland ..260/309.6234,926 3/ l 945 Switzerland ..260/ 309.6

OTHER PUBLICATIONS Primary Examiner -Natalie Trousof Attorney-Johnston,Root, OKeeffe, Keil, Thompson & Shurtlefi' [57] ABSTRACT Production of2-carbamyl-2-imidazolines by reacting haloacetamides with 1,2-a1kylenediamines and elementary sulfur, and the 2-carbamyl-2-imidazolines. Thenew compounds are auxiliaries for the textile and leather industries,plant protection agents and valuable starting material for themanufacture of textile and leather auxiliaries and plant protectionagents.

6 Claims, No Drawings Z-CARBAMYL-Z-IMHDAZOLINES AND METHOD F OR THEIRPRODUCTION This invention relates to a process for the production ofcarbamyl-Z-imidazolines by reaction haloacetamides with l,2-alkylenediamines and elementary sulfur. The invention also relates to newsubstances of this kind.

The Berichte der Deutschen Chemischen Gesellschaft, 24, 1846 (1891) and25, 2132 et seq. (1892) disclose that imidazolines which are substitutedin the 2-position may be made by reacting thioamides with ethylenediamine. Other methods of manufacture are summarized in A. Weissbergersmonograph lmidazole and its Derivatives, Part I (1953, lntersciencePublishers, lnc., New york, London), pp. 213-218. 2-1midazolinessubstituted in the 2-position by a carbonamide function have not beenhitherto described in the literature.

It is an object of the present invention to provide a new process forthe production of 2-carbamyl-2- imidazolines in a more economical mannerand in good yield and high purity.

A further object of this invention is to provide the new2-carbamyl-2-imidazolines themselves.

These and other objects are achieved and Z-carbamyl-2-imidazolines ofthe general formula:

where R, R and R, which may be the same or different, stand for hydrogenor an aliphatic or cycloaliphatic radical and in which R may also standfor an araliphatic or aromatic radical or R and R may be joined to theadjacent nitrogen atom to form a heterocyclic ring, are advantageouslyproduced by reacting haloacetamides of the general formula where R and Rhave the meanings stated above, X is a halogen atom and Y is hydrogen ora halogen atom, with 1,2-alkylene diamines of the general formula:

I{1NCIJII-(JHNHQ TIT wherein each R has the meaning stated above, andelementary sulfur.

The reaction may be represented by the following formulas, whichillustrate the use of N-n-butylchloroacetamide (reaction 1) andN-n-butyldichloracetamide (reaction 2) respectively:

i H I u o N Compared with the prior art the process of the inventionprovides a large number of 2carbamyl-2- imidazolines in good yield and ahigh degree of purity in a simpler and more economical manner.

Preferred haloacetamides of the general formula II, preferred1,2-alkylene diamines of the general formula III and accordinglypreferred end products I are those in the formulas of which the radicalsR, R and R, which may be the same or different, stand for hydrogen oralkyl radicals of from one to 18 carbon atoms, most preferably of fromone to 12 carbon atoms, or cycloalkyl radicals of from five to 12 carbonatoms and additionally R may stand for an optionally substituted benzylor phenyl radical or R and R may be joined to the adjacent nitrogen atomto form a five or six membered heterocyclic ring which may contain inaddition to the said nitrogen atom a further nitrogen atom or an oxygenatom, and X stands for chlorine and Y stands for hydrogen or chlorine.The said radicals and the heterocyclic ring may be further substitutedby groups and/or atoms which are inert under the conditions of reaction,such as alkyl and alkoxy groups of from one to four carbon atoms andalkoxy-alkyl groups of from two to four atoms. The said araliphatic oraromatic radical may carry similar substituents. The starting materialsII and III and the elementary sulfur are normally reacted instoichiometric amounts. It is also possible to use starting material 111and/or the sulfur in excess, say up to 1.5 times, based on the startingmaterial 11.

The starting material III used for binding the halogen hydracid formedmay be replaced by an equivalent amount of any base capable of bindinghalogen hydracid. Examples of such bases are tertiary amines such astriethylamine; and oxides and hydroxides of alkali and alkaline earthmetals such as sodium hydroxide, potassium hydroxide and calcium oxide.

The following compounds are examples of suitable starting materials 11and Ill: monochloro-, dichloro-, bromo-, iodoand chlorobromo-acetamides;corresponding N-butyl, N-(3-chloro-4-methyl-phenyl), N- cyclohexyl,N,Ndi-n-propyl, N,N-di-cyclohexyl, N- methyl-N-cyclohexyl, N-dodecyl,N-stearyl, N-(2,4- dichlorophenyl) and N-benzyl compounds; and analogoustertiary amides with morpholine, piperidine and piperazine;1,2-diamino-ethane, 1,2-diaminopropane, 1,2-diamino-n-butane,2,3-diamino-butane, l,Z-diamino-l-cyclohexyl-ethane and3,4-diamino-hexane.

The reaction is normally carried out at a temperature between 50 and 180C and preferably between and C, at atmospheric or elevated pressure,continuously or batchwise. It is convenient to use organic solventswhich are inert under the conditions of reaction, such as aromatichydrocarbons, e.g., benzene, toluene and xylene; alkanols such asethanol, npropanol, isobutanol, n-butanol; cyclic ethers such asdioxane; glycol ethers, particularly when elevated temperatures areused, such as ethylene glycol mono( methyl-or ethyl) ether and1,2-propylene glycol diethyl ether; and appropriate mixtures thereof.The molar ratio of solvent to starting material II is preferably 1-1021.

The reaction may be carried out as follows:

a mixture of the starting material 11, sulfur and, optionally, solventis prepared and starting material III is added thereto portionwise over1 to 2 hours with thorough mixing. When no more hydrogen sulfide isevolved, the mixture is filtered and the desired product is separatedfrom the filtrate in conventional manner, for example bycrystallization, if necessary after driving off the solvent.

The new compounds obtainable from the process of the invention areauxiliaries for the textile and leather industries, plant protectionagents and also valuable intermediates in the manufacture of textile andleather auxiliaries and plant protection agents. Thus they may be usedto give synthetic fibrous materials such as polyesters and polyamides anantistatic finish. Moreover, the substances of the invention, when usedin quantities ranging from 5 to 50 g/kg of fibrous material, provide inaddition to the antistatic effect a soft or firm handle of the finishedtextile material depending on the constitution of the compound.Preferred compounds for this use are 2-carbamyl-2- imidazolines of thegeneral formula 1 in which the radicals R, R and R are the same ordifferent and stand for hydrogen atoms, alkyl radicals of from one to 18carbon atoms or cycloalkyl radicals of from five to 12 carbon atoms, andR may also stand for an optionally substituted benzyl or phenyl radicalor R and R may be joined to the adjacent nitrogen atom to form a five orsix membered heterocyclic ring, which may contain in addition to thesaid nitrogen atom a further nitrogen atom or an oxygen atom.

In the following Examples the parts are by weight.

EXAMPLE 1 in a stirred apparatus there are dissolved 75 parts ofN-butyl-chloroacetamide and 32 parts of sulfur in 500 parts of toluene.To this mixture there are slowly added over a period of 2 hours and at atemperature of 100 C 65 parts of ethylene diamine. On termination of theevolution of hydrogen sulfide (after about 3 hours), the hot toluenesolution is decanted from the precipitated ethylene diaminehydrochloride and then filtered and cooled to about 5-l0 C. Theprecipitated final product is filtered off, washed with a little acetoneand dried. There are thus obtained 74 parts ofZ-(N-butylcarbamyl)-2-imidazoline, m.p. 165 C. This corresponds to ayield of 87 percent of theory.

EXAMPLE 2 In a stirred apparatus 109 parts of N-( 3-chloro-4-methylphenyl)-chloroacetamide and 32 parts of sulfur are heated in 800parts of toluene at 105 C and 65 parts of ethylene diamine are slowlyadded over 2 hours. The reaction mixture is then stirred for a furtherperiod of approximately 4 hours at a temperature of 110 C. After workingup in a manner similar to that described in Example 1 there are obtained98 parts of 2-( N-3-chloro-4-methylphenyl-carbamyl )-2- imidazoline, mp.166-167 C. After recrystallizing from dimethyl formamide the compoundhas m.p. 168 C. The yield is 82 percent of theory.

EXAMPLE 3 ln a stirred vessel 84 parts of N-dodecylchloroacetamide and21 parts of sulfur dissolved in 800 parts of toluene are heated at C. 45Parts of ethylene diamine are slowly added over 1 hour, and the mixtureis then stirred at C for a further 6 hours. After working up in a mannersimilar to that described in Example 1 there are obtained 76 parts of2-(N-dodecylcarbamyl)-2-imidazoline, m.p. 143-145 C. The yield is 81percent of theory.

EXANIPLE 4 Example 1 is repeated except that 86 parts of N-stearylchloroacetamide are reacted with 16 parts of sulfur and 33 partsof ethylene diamine in 500 parts of toluene. There are obtained 74 partsof 2-(N-stearylcarbamyl)-2-imidazoline, m.p. 135-136 C, corresponding toa yield of 81 percent of theory.

EXAMPLE 5 In a process similar to that described in Example 1 60 partsof N-(2,4-dichlorophenyl)chloroacetamide are reacted with 16 parts ofsulfur and 33 parts of ethylene diamine in 500 parts of toluene. Thereare obtained 58 parts of 2-( N-2,4-dichlorophe nylcarbamyl )-2imidazoline, m.p. 171 C, corresponding to a yield of 90 percent oftheory.

EXAMPLE 6 Example 1 is repeated except that 46 parts of N-benzylchloroacetamide are reacted with 16 parts of sulfur and 33 partsof ethylene diamine in 500 parts of toluene. There are obtained 45 partsof 2-(N-benzylcarbamyl)-2-imidazoline, rn.p. l80-l91 C, corresponding toa yield of 88 percent of theory.

EXAMPLE 7 in a stirred vessel 67 parts of N-isopropyl chloroacetamideand 32 parts of sulfur dissolved in 600 parts of isobutanol are heatedat 100 C. To this mixture there are slowly added 74 parts of1,2-propylene diamine, and the mixture is then stirred under reflux fora further 6 hours. After removing the hydrochloride, the solvent isdistilled off and the residue is recrystallized from ligroin. There arethus obtained 78 parts of 2-(N-isopropylcarbamyl)-4-methyl-2-imidazoline, m.p. -l21 C, correspondingto a yield of 92 percent of theory.

EXAMPLE 8 In a manner similar to that described in Example 7 87 parts ofN-cyclohexylchloroacetamide are reacted with 32 parts of sulfur and 74parts of 1,2-propylene diamine. There are obtained 90 parts of 2-(N-cyclohexylcarbamyl)-4-methyl-2-irnidazoline, m.p. 1261 28 C,corresponding to a yield of 86 percent of theory.

What we claim is:

l. A 2-carbamyl-2-imidazoline of the formula wherein the groups Rrespectively denote hydrogen, lower alkyl or cyclohexyl and R denoteshydrogen, alkyl of one to 18 carbon atoms, cycloalkyl of five to 12carbon atoms, phenyl, benzyl, chlorotolyl or chlorophenyl.

2. A process for the production of a 2-carbamy1-2- imidazoline of theformula:

where R and R have the meanings stated above and where X is a halogenatom and Y is hydrogen or a halogen atom, with a 1,2-a1kylene diamine ofthe formula:

where the groups R have the meaning stated above, and at least astoichiometric amount of elementary sulfur.

3. A process as claimed in claim 2 wherein the reaction is carried outwith one or both of the diamine and the sulfur present in excess up to1.5 times, based on the haloacetamide.

4. A process as claimed in claim 2 wherein the reaction is carried outat a temperature between 50 and 1 C.

5. A process as claimed in claim 2 wherein the reaction is carried outat a temperature between 80 and C.

6. A process as claimed in claim 2 wherein the reaction is carried outin an organic solvent which is inert under the conditions of reactionand which is present in a ratio of from 1 to 10 moles of solvent to 1mole of the haloacetamide.

2. A process for the production of a 2-carbamyl-2-imidazoline of the formula: where the groups R1 respectively denote hydrogen, lower alkyl or cyclohexyl, R2 and R3 respectively denote hydrogen, alkyl of one to 18 carbon atoms, cycloalkyl of five to 12 carbon atoms, phenyl, tolyl, chlorophenyl, chlorotolyl or benzyl, or R2 and R3 together with their nitrogen atom denote morpholyl, piperidyl or piperazyl, which comprises reacting a haloacetamide of the formula: where R2 and R3 have the meanings stated above and where X is a halogen atom and Y is hydrogen or a halogen atom, with a 1,2-alkylene diamine of the formula: where the groups R1 have the meaning stated above, and at least a stoichiometric amount of elementary sulfur.
 3. A process as claimed in claim 2 wherein the reaction is carried out with one or both of the diamine and the sulfur present in excess up to 1.5 times, based on the haloacetamide.
 4. A process as claimed in claim 2 wherein the reaction is carried out at a temperature between 50* and 180* C.
 5. A process as claimed in claim 2 wherein the reaction is carried out at a temperature between 80* and 150* C.
 6. A process as claimed in claim 2 wherein the reaction is carried out in an organic solvent which is inert under the conditions of reaction and which is present in a ratio of from 1 to 10 moles of solvent to 1 mole of the haloacetamide. 